Azo dyestuffs insoluble in water and fiber dyed therewith



Patented May 7, 1940 UNITED STATES PATENT OFFICE AZO DYESTUFFS INSOLUBLEIN WATER AND FIBER- DYED THEREWITH Walter Broker, Offenbach-on-the-Main,Germany, assignor to General Aniline & Film Corporation, a corporationof Delaware No Drawing. Application December 23, 1938,

Serial No. 247,407. 1937 The present invention relates to azo dyestuffsinsoluble in water and to'fiber dyed therewith; more particularly, itrelates to azo dyestuffs of the following general formula:

amino-2-benzoy1-diphenylamine or a substitution product thereof with anarylide of 2.3-hydroxynaphthoic acid.

In German patent specification No. 620,460 and French patentspecification No. 37,511 is disclosed a manufacture of water-insolubleazo-dyestuffs by coupling with a 2.3-hydroxynaphthoic acid arylide adiazo-compound from a 4-aminodiarylamine containing in 2-position afunctional derivative of the carboxyl group, such as an ester or asubstituted amide, blue dyestuffs being generally obtained. Whencompared with these known dyestuffs, the new dyestuffs ,which throughoutyield deep-black tints, are distinguished by a better tinctorial"strength and improved properties of fastness.

The new dyestufis may, with special advantage, be used for theproduction of fast prints.

The 4-amino-2-benzoy1-diphenylamines used as diazo-components in thepresent process may be prepared by condensing l-benzoyl-2-chloro-5-nitrobenzene and the substitution products thereof obtainable accordingto known processes (op. Berichte der Deutschen Chemischen Gesellschaft,vol. 31 (1898), page 1695) with aniline and the substitution productsthereof and reducing subsequently the 4-nitro-2-benzoyl-diphenylaminesthus obtained.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto; the parts are by weight:

1. Bleached cotton fabric is padded with a solution containing per liter15 parts of 1-(2'.3'- hydroxynaphthoylamino) 2 methylbenzene, 29

g parts of a caustic soda solution of 34 B. and

In Germany December 24,

10 Claims. (01. 260-203) 20 parts of Turkey red oil and dried. Thefabric thus treated is then printed with the following printing paste:

, Parts The diazonium zinc chloride compound from4-amino-Z-benzoyl-diphenylamine- 22 Acetic acid of per cent strength 40Water 438 Starch tragacanth thickening 500 The material is then dried,passed through a solution containing per liter 2 grams of sodiumcarbonate and having a temperature of C. to 0., rinsed and soaped atboiling temperature.

A deep-black print is obtained. In the same manner the dyestuff can beproduced on viscose artificial silk or on mixed fabrics from cotton andviscose artificial silk.

The dyestuff is characterized by the following formula:

(lo-O 2. Cotton piece goods are impregnated with a solution containingper liter 15 parts of 1-(2'.3'-

hydroxy naphthoyl amino) 4 chlorobenzene, dried and printed with thefollowing paste:

' Parts The diazonium zinc chloride compound from 4-amino-4'-methoxy-2(4 -methoXy-benzoyl) -diphenylam ine 20 Water 450 Starch tragacanththickening 500 Acetic acid of 50 per cent strength 30 at 15 0., into asolution prepared from 35.8 parts of 1 -(2'.3 hydroxynaphthoylamino) 2.4dimethoxy-5-chlorobenzene, parts of caustic soda solution of 34 B., 5parts of Turkey red oil and 1500 parts of water. When the introductionis finished, the whole is further stirred for minutes, then renderedalkaline by means of a sodium carbonate solution, further stirred for 30minutes, filtered with suction and the solid matter washed untilneutral. The black dyestuff thus obtained is preferably worked up in theform of a paste and yields, With the usual substrata, valuable colorlakes.

The following table illustrates a number of other dyestuffs obtainableaccording -to this invention:

2. The water-insoluble azo dyestufis of .the following general formula(Jo-Oar Diazo-component4-amIi)no-2-(4-dimethylaminobenzoyl)-diphenylamine 0 4-am]i)no-4'-metl1oxy-2- (4"-methylbenzoyl) -diphenylamine Do4-amino-4-benzyloxy-Z-benzoyl-diphenylamine4-amino-2-ethoxy-Z-benzoyl-diphenylamine4-amino-4-chloro-2-benzoyl-diphenylamine4-amino-2-methoxy-5-methyl-2-benzoyl-diphenylamine4-a'mino-6-methyl-2-benzoyl-diphenylamine4-amino-4-methoxy-2-benzoyl-diphenylamine4-a1nino-4'-ethoxy-2-benzoyl-diphenylamine l 4-amino-2-(4-methoxy-benzoyl)-diphenylamine 4-amino-2-(4"-ethoxy-benzoyl) -diphenylamine4 amino 4 methoxy 2 (4 ethoxy benzoyl) diphenylamine.

o 4-ami1ID1o-2 4-dimethoxy-Z-benzoyl-dipheny1amin4-amino-3-mcthy1-2-bcnzoyl-diphenylamine l t4-amino-2-(4"-diethy1-ami.nobenzoyl)-diphenylam1ne Since an object ofthe present invention is to produce dyestufis of good fastnessproperties which dyestufis are insoluble in water, it is to beunderstood that the aromatic nuclei of the general formula appearing inthe appended claims do not contain any substituents which are known torender the dyestuffs soluble in water. Substituents of this kind are,for instance, the sulfonic acid and carboxylic acid group.

I claim:

1. The water-insoluble azo dyestufi's of the following general formulaCO Y OO.NH.R

wherein X1 stands for a member of the group consisting of hydrogen andalkoxy, X2 for a member of the group consisting of hydrogen, alkoxy,halogen and benzyloxy, X: for a member of the group consisting ofhydrogen and methyl, at least one X being hydrogen, Y stands for amember of the group consisting of hydrogen, alkoxy, methyl anddialkylamino, Z for a member of the group consisting of hydrogen andmethyl, and R means a member of the group consisting of radicals of thebenzene and naphthalene series, yielding, when produced on the fiber,black dyeings of good fastness properties, particularly of very goodfastness to washing, and of great tinctorial strength.

and. R means a memberof the group consisting of radicals of the benzeneand naphthalene series,

yielding, when produced on the fiber, black dyeings of good fastnessproperties, particularly of very good fastness to washing, and of greattinctorial strength.

3. The water-insoluble azo dyestuff of the following formula yielding,when produced onthe fiber, deep-black dyeings of good fastnessproperties, particularly of very good fastness to washing, and of greattinctorial strength.

4. The water-insoluble azo dyestufi of the following formula yielding,when produced on the fiber, reddish black dyeings of good fast-nessproperties, par-s ticularly'of very good fastness to washing, and

yielding, when produced on the-fiber, deep black.

,dyeings of good fastness properties, particularly of very good fastnessto washing, and of great,

tinctorial strength.

6. Fiber dyed with the water-insoluble azo dyestuffs as claimed in claim1.

7. Fiber dyed with the water-insoluble azo dyestuffs as claimed in claim2. 8. Fiber dyed with the water-insoluble azo dyestufi" as claimed inclaim 3.

9. Fiber dyed with the water-insoluble azo dyestufi as claimed in claim4.

10. Fiber dyed with the water-insoluble dyestufi as claimed in claim 5.

WALTER BRKER.

